A perovskite module laser scribing method capable of real-time detection

Abstract

The application discloses a perovskite module laser scribing method capable of real-time detection and relates to the technical field of batteries. The method shortens P1 scribing, cooperates with the setting of P2 scribing, P3 scribing and a vertical cutting line, realizes the partition of TCO, forms a detection area and an effective area, and makes the detection and the effective area independent and not interfere with each other. The detection area can be detected in real time after P2 scribing and P3 scribing. The application can realize real-time, nondestructive and quantitative detection of P2 and P3 scribing quality, quickly adjust laser parameters, form a closed-loop mass production process, and improve module yield, efficiency and reliability without affecting the power generation structure and performance of the effective area. The application effectively solves the problems of offline detection of P2, difficulty in verifying damage of TCO caused by over-etching of P3, detection lag and low batch yield.

Description

Technical Field

[0001] This invention relates to the field of battery technology, and more specifically, to a laser scribing method for perovskite modules that can be detected in real time. Background Technology

[0002] Perovskite solar cells have become a key area for industrialization in the photovoltaic field due to their advantages such as high efficiency, low cost, simple fabrication process, and ability to be fabricated on a large scale. Laser scribing technology is the core process for realizing the series connection of sub-cells in perovskite modules and ensuring the electrical performance of the module. It mainly includes three key processes: P1, P2, and P3. Please refer to [link / reference needed]. Figure 1 and Figure 2 : P1 is the bottom electrode isolation line, used to divide the transparent conductive oxide (TCO) layer and form the bottom electrode region of the independent sub-cell. P2 is an interlayer conductive line used to etch through all functional layers (hole transport layer, perovskite layer, electron transport layer, upper and lower passivation layers, etc.), while retaining the TCO layer, to achieve effective conduction between the top electrode and the bottom electrode of the adjacent sub-cell. P3 is the top electrode isolation line, used to separate the metal top electrode and ultimately complete the series structure of the sub-cells.

[0003] The existing conventional fabrication process is as follows: P1 scribing, functional layer fabrication (hole transport layer, electron transport layer, perovskite active layer, upper passivation, lower treatment, etc.), P2 scribing, metal electrode fabrication, P3 scribing, edge cleaning, and encapsulation. This process has significant deficiencies in both P2 scribing quality control and P3 scribing damage detection, as detailed below: In traditional processes, P1 and P2 have the same length, and the spacing between the three scribing lines (P1, P2, and P3) is extremely small (10-100μm). This makes it impossible to measure the resistance on both sides of the P2 channel, and thus impossible to determine online whether P2 has been over-scribed. If the scribing power of P2 is too high, it will scribe through the underlying TCO layer, directly causing leakage and open circuits between sub-cells, leading to module failure. The above problems can only be inferred through reverse engineering after the module is fully manufactured, which results in detection delays and easily leads to batch product losses and increased costs.

[0004] P3 scribing is used to isolate the metal top electrode, but excessive laser power can damage or even break the underlying TCO layer, leading to leakage at the sub-cell edges, decreased parallel resistance, and in severe cases, open circuits between sub-cells. Current processes lack effective methods to specifically detect whether P3 scribing damages the TCO, making it impossible to distinguish between moderate and excessive P3 scribing and the TCO state. Related defects can only be indirectly assessed after packaging through efficiency and aging tests, resulting in delayed detection, low reliability, and difficulty in meeting the precise quality control requirements of mass production.

[0005] Currently, the conventional testing methods for the scribing quality of P2 and P3 perovskite modules mainly include overall module IV testing, probe station resistance measurement, optical microscope morphology observation, and electroluminescence (EL) detection; advanced testing methods include photocurrent imaging (LBIC), light-induced thermal imaging (LIT), and scanning electron microscopy (SEM) cross-sectional analysis.

[0006] Among them, IV testing and EL testing can only be used to judge the overall performance after the module is fully manufactured, and cannot identify the failure of a single scribing line in real time; probe station resistance measurement is limited by the extremely small scribing line spacing, and the probe cannot make precise contact measurement; optical and SEM observation are offline and destructive tests, which are inefficient and costly; high-end equipment such as LBIC and LIT are expensive and slow, and can only be used for laboratory sampling, and cannot be used for full inspection on large-scale production lines.

[0007] In summary, existing testing solutions generally suffer from problems such as detection lag, inability to accurately locate faults, difficulty in distinguishing failure types, high costs, or poor compatibility. They cannot achieve real-time, non-destructive, and full-coverage testing of P2 and P3 scribing quality, which seriously restricts quality control and yield improvement in the industrialization process of perovskite photovoltaic modules.

[0008] In view of this, the present invention is proposed. Summary of the Invention

[0009] The purpose of this invention is to provide a laser scribing method for perovskite modules that can be detected in real time.

[0010] This invention is implemented as follows: In a first aspect, the present invention provides a real-time detectable laser scribing method for perovskite modules, comprising: P1 channels are formed by scribing P1 lines on a TCO substrate, wherein the length of the P1 scribing lines is less than the length of the TCO substrate. A functional layer is deposited on the TCO substrate after the P1 scribing, and then a P2 scribing is performed to form a P2 channel. The P2 channel scribes through the functional layer without damaging the TCO substrate. The length of the P2 scribing is greater than the length of the P1 scribing and less than or equal to the length of the TCO substrate. A cutting line perpendicular to the P1 channel is prepared at the shortened end of the P1 scribe line. The cutting line pierces through the functional layer and the TCO substrate. The cutting line divides the module into an effective area, a first detection area, and a second detection area. The lengths of the first detection area and the second detection area are not both 0. The effective area retains complete P1 and P2 channels. At least one of the first and second detection areas does not have a P1 channel and only includes a P2 channel. The channel resistance on both sides of the P2 channel is measured in the detection area, and the channel resistance is compared with the initial resistance value of TCO to determine the etching quality of the P2 scribing. Subsequently, a metal top electrode is deposited by vapor deposition, and a P3 scribe line is made on the metal top electrode to divide the metal top electrode. The length of the P3 scribe line is greater than the length of the P1 scribe line and less than or equal to the length of the TCO substrate. The effective area retains complete P1 channels, P2 channels and P3 channels. At least one of the first detection area and the second detection area has no P1 channel, and the first detection area and the second detection area each independently include a P2 channel or a P3 channel, or the first detection area and the second detection area simultaneously include both P2 channels and P3 channels. Before or after the P3 scribing, a protective line is formed at the location of the scribe line, penetrating the metal top electrode, the functional layer, and the TCO substrate; The resistance between the left side of the P2 channel and the right side of the P3 channel is measured in the first detection area or the second detection area containing the P3 channel, or the resistance on both sides of the P3 channel is measured to obtain the surface resistance of the metal electrode. The presence or absence of metal residue in the P3 channel is determined based on the value of the surface resistance of the metal electrode. After removing the functional layer of the first or second detection area, the resistance between the left side of the P2 channel and the right side of the P3 channel is measured, or the resistance on both sides of the P3 channel is measured to obtain the TCO surface resistance; the TCO surface resistance is compared with the initial resistance value of the TCO to determine whether the P3 channel has damaged the TCO substrate. After passing the inspection, the edges of the effective area are cleaned, and then the perovskite module is packaged to complete the preparation.

[0011] In an optional implementation, the length of the P1 scribe line is 70%-95% of the length of the TCO substrate.

[0012] In an optional implementation, the length of the P1 line can be adjusted by shortening one side or by shortening both sides simultaneously.

[0013] In an optional embodiment, the width of the cutting line is 5-200 μm.

[0014] In an optional embodiment, the width of the protective line is 1-5 mm wider than the width of the cutting line.

[0015] In an optional implementation, the method of forming the protective line before the P3 scribing includes: using a mask to completely cover the area of ​​the cutting line, the width of the mask being greater than the width of the cutting line; subsequently depositing the metal top electrode, the metal top electrode covering the entire area except for the area covered by the mask; and performing the P3 scribing after removing the mask, the area covered by the mask being the protective line.

[0016] In an optional embodiment, the method of forming the protective line after the P3 scribing includes: after the P3 scribing, scribing through all film layers at the position of the cutting line with a laser, wherein the width of the laser scribing is greater than the width of the cutting line, and the area formed by the laser scribing is the protective line.

[0017] In an optional implementation, the step of comparing the channel resistance with the initial resistance value of TCO to determine the P2 etching quality includes: If the difference between the channel resistance and the initial resistance of the TCO is 0-1Ω, then the test is qualified; If the difference between the channel resistance and the initial resistance of the TCO is greater than 1Ω or less than 0Ω, the test is unqualified and the P2 scribing parameters need to be readjusted.

[0018] In an optional implementation, the step of determining whether there is metal residue in the P3 channel based on the surface resistance value of the metal electrode includes: If the surface resistance of the metal electrode is measured to be a finite value, it indicates that metal electrode material remains inside the P3 channel, the scribing did not completely cut off the metal top electrode, and there is a metal residue defect. If the measured surface resistance of the metal electrode exceeds the range of the detection equipment and is in an open-circuit high-resistance state, it indicates that the metal electrode in the P3 channel has been completely etched away, the metal top electrode is completely disconnected, and there is no metal residue in the channel.

[0019] In an optional implementation, the step of comparing the TCO surface resistance with the initial TCO resistance to determine whether the P3 scribing has damaged the TCO substrate includes: If the difference between the surface resistance of the TCO and the initial resistance of the TCO is 0-1Ω, then the test is qualified; If the difference between the surface resistance of the TCO and the initial resistance of the TCO is greater than 1Ω or less than 0Ω, the test is unqualified and the P3 scribing parameters need to be readjusted.

[0020] The present invention has the following beneficial effects: The laser scribing method for real-time detection of perovskite modules provided by this invention shortens the P1 scribing line and, in conjunction with the P2 scribing line, P3 scribing line, and vertical cutting line, achieves TCO partitioning, forming an effective area, a first detection area, and a second detection area. This ensures that the detection and power generation effective areas are independent and do not interfere with each other. The first and second detection areas can be detected in real time after the P2 and P3 scribing lines are drawn. Specifically, in the first or second detection area without P1, the resistance of the P2 channel is measured to determine the conduction state of P2 and whether the TCO has been over-etched and damaged. In the detection area without P1 or without P1 and P2, the resistance between the left side of the P2 channel and the right side of the P3 channel is measured, or the resistance on both sides of the P3 channel is measured to obtain the surface resistance of the metal electrode and the surface resistance of the TCO, thereby determining whether there is metal residue on P3 and whether the underlying TCO layer has been over-etched and damaged. This invention enables real-time, non-destructive, and quantitative detection of the P2 and P3 marking quality without affecting the effective power generation structure and performance. It allows for rapid adjustment of laser parameters, forming a closed-loop mass production process and improving module yield, efficiency, and reliability. It effectively solves problems such as the inability to detect P2 online, difficulty in verifying the Total Cost of Production (TCO) of P3 over-marking damage, detection lag, and low batch yield in the process. Attached Figure Description

[0021] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 Schematic diagram of cross-sections P1, P2, and P3 prepared for conventional laser scribing; Figure 2 A schematic diagram of the planar preparation of P1, P2, and P3 for conventional laser scribing; Figure 3 This is a schematic diagram of the structure of short P1 prepared by laser scribing in Example 1; Figure 4 This is a schematic diagram of the structure of P2 prepared by laser scribing in Example 1; Figure 5 This is a schematic diagram of the structure for preparing the cutting line using laser scribing in Example 1; Figure 6 This is a cross-sectional schematic diagram of the effective area segmented by the cutting line in Example 1; Figure 7 This is a schematic cross-sectional view of the detection area divided by the cutting line in Example 1; Figure 8 This is a schematic diagram of measuring the channel resistance of P2 in Example 1; Figure 9This is a schematic diagram of the mask blocking the cutting line in Example 1; Figure 10 This is a schematic diagram of the metal top electrode coverage and the actual effective area in Example 1; Figure 11 This is a schematic diagram of the actual effective area cross-section in Example 1; Figure 12 This is a schematic diagram of the cross-section of the detection area in Example 1; Figure 13 This is a schematic diagram of the test points for the surface resistance of the metal electrode in Example 1; Figure 14 This is a schematic diagram of the test points for the surface resistance of the TCO in Example 1; Figure 15 This is a schematic diagram showing the shortening of one side of the line drawn on P1 in Example 2; Figure 16 This is a schematic diagram of the test point location marked with line P2 in Example 2; Figure 17 This is a schematic diagram of the actual effective area in Example 2; Figure 18 This is a schematic diagram showing the shortening of one side of the line drawn on P2 in Example 3; Figure 19 This is a schematic diagram of the effective area, the first detection area, and the second detection area in Example 3; Figure 20 This is a schematic diagram of different areas after the line P3 is drawn in Example 3; Figure 21 This is a schematic diagram of the test points for the surface resistance of the metal electrode in Example 3; Figure 22 This is a schematic diagram of the test points for the TCO surface resistance in Example 3; Figure 23 This is a schematic diagram showing the entire area covered by the maskless metal electrode in Example 4; Figure 24 This is a schematic diagram showing the positions of the protective line and the cutting line in Example 4.

[0023] Icon: 100 - Perovskite Module; 111-TCO substrate; 112-Electron transport layer; 113-Perovskite layer; 114-Hole transport layer; 115-Metallic top electrode; 121-P1 channel; 122-P2 channel; 123-P3 channel; 131 - Cutting line; 132 - Effective area; 1321 - Actual effective area; 133 - Detection area; 1331 - First detection area; 1332 - Second detection area; 134 - Mask; 135 - Laser scribing. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0025] Please see Figures 3-22 This invention provides a real-time detectable laser scribing method for perovskite modules, comprising: S1. A P1 channel 121 is formed by scribing a P1 line on the TCO substrate 111. The length of the P1 scribing line is less than the length of the TCO substrate 111.

[0026] Normally, the length of the P1 scribing is equal to the length of the TCO substrate 111. In this invention, by shortening the length of the P1 scribing, some blank areas on the TCO substrate 111 are left un-scribed. Specifically, the length of the P1 scribing is 70%-95% of the length of the TCO substrate 111. That is, in this invention, the length of the P1 scribing is shortened by 5%-30% compared to the normal length. The shortening can be achieved by shortening one side or by shortening both sides simultaneously. When shortening one side, only one side of the TCO substrate 111 is blank; when shortening both sides simultaneously, both sides of the TCO substrate 111 have blank areas.

[0027] S2. A functional layer is deposited on the TCO substrate 111 after P1 scribing, and then P2 scribing is performed to form P2 channel 122. P2 channel 122 scribes through the functional layer without damaging the TCO substrate 111. The length of P2 scribing is greater than the length of P1 scribing and less than or equal to the length of TCO substrate 111.

[0028] The functional layers in this invention include, but are not limited to, hole transport layer 114, perovskite layer 113, electron transport layer 112, upper and lower passivation layers, etc. The deposition methods and materials of each functional layer are conventional choices, and no specific restrictions are imposed in this invention.

[0029] In this invention, the length of the P2 scribe line is greater than the length of the P1 scribe line and less than or equal to the length of the TCO substrate 111. This ensures that at least the P2 channel 122 is present in the blank area of ​​the TCO substrate 111, which facilitates the subsequent detection of the channel resistance formed by the P2 channel 122.

[0030] S3. A cutting line 131 perpendicular to the P1 channel 121 is prepared at the shortened end of the P1 scribing. The cutting line 131 pierces through the functional layer and the TCO substrate 111. The cutting line 131 divides the module into an effective area 132 and a detection area 133. The effective area 132 retains the complete P1 channel 121 and P2 channel 122. The detection area 133 includes a first detection area 1331 and a second detection area 1332. The lengths of the first detection area 1331 and the second detection area 1332 are not both 0. When one of them is 0, it indicates that the P1 scribing is shortened at one end. At least one of the first detection area 1331 and the second detection area 1332 does not have the P1 channel 121 and only includes the P2 channel 122.

[0031] In this invention, the functional layer and the TCO substrate 111 are etched through by a cutting line 131, so that the effective area 132 and the detection area 133 are completely isolated and there is no connection. The width of the cutting line 131 is 5-200μm.

[0032] It should be noted that when the P1 line is shortened on one side, the TCO substrate 111 is divided into an effective area 132 and a detection area 133; when both sides are shortened simultaneously, the TCO substrate 111 is divided into an effective area 132 in the middle and two detection areas 133 on both sides (first detection area 1331 and second detection area 1332). When there is only one detection area 133, the P2 channel 122 must exist within the detection area 133. When there are two detection areas 133, the P2 channel 122 can exist in one of the first detection area 1331 and the second detection area 1332, while the other remains blank, to facilitate the subsequent P3 channel 123.

[0033] S4. Measure the channel resistance on both sides of the P2 channel 122 in the first detection area 1331 or the second detection area 1332 containing the P2 channel 122, and compare the channel resistance with the initial resistance value of TCO to determine the etching quality of the P2 scribing. The channel resistance on both sides of the P2 channel 122 is measured using a milliohmmeter, and the total resistance is recorded. Since there are multiple P2 channels 122 on the detection area 133, both sides of each P2 channel 122 need to be tested. By comparing the channel resistance on both sides of the multiple P2 channels 122 laterally, the stability of the laser equipment can be determined. Furthermore, the steps to determine the P2 etching quality by comparing the channel resistance with the initial TCO resistance include: (1) If the difference between the channel resistance and the initial resistance of the TCO is 0-1Ω, the test is qualified; The smaller the difference between the channel resistance and the initial resistance of the TCO, the better the product. Specifically, a difference between 0 and 0.3 Ω indicates a superior product. At this point, the laser just penetrates the functional layer, the TCO remains intact, the ohmic contact between Cu and TCO is optimal, and series loss is minimal, making it the preferred choice for mass production. A difference between 0.3 and 1.0 Ω also indicates a qualified product, but with slight TCO surface burns / interface oxidation, which slightly increases the contact resistance.

[0034] (2) If the difference between the channel resistance and the initial resistance of TCO is greater than 1Ω or less than 0Ω, the test is unqualified and the P2 scribing parameters need to be readjusted.

[0035] When the difference between the channel resistance and the initial resistance of the TCO is greater than 1Ω, it indicates that the laser over-etching has damaged the conductive layer of the TCO, the local TCO has become thinner or micro-broken, the interconnect series resistance has soared, the fill factor has deteriorated significantly, and the TCO is directly rejected.

[0036] When the difference between the channel resistance and the initial resistance of the TCO is less than 0Ω, it indicates that there is residual perovskite in P2 or the transport layer is not cleanly etched, or the functional layer is short-circuited, which is also a defect.

[0037] The initial resistance of TCO can be measured before coating and scribing. It is measured using two probes at a fixed and uniform test spacing (consistent with the subsequent P2 / P3 channel test point spacing); or refer to the nominal value in the TCO datasheet. The nominal sheet resistance of TCO is only used as a selection reference and not as the initial judgment benchmark resistance value.

[0038] By setting up a detection area 133, this invention can immediately detect the channel resistance of the P2 channel 122 after the P2 marking is completed, without having to reverse-engineer through overall performance testing after the module is fully manufactured. When the channel resistance of the P2 channel 122 does not meet the standard, it can be adjusted in time, avoiding product losses such as subsequent metal top electrode 115 and P3 marking.

[0039] S5. Subsequently, a metal top electrode 115 is deposited by vapor deposition. A P3 scribe line is made on the metal top electrode 115 to form a P3 channel 123 to divide the metal top electrode 115. The length of the P3 scribe line is greater than the length of the P1 scribe line and less than or equal to the length of the TCO substrate 111. The effective region 132 retains complete P1 channel 121, P2 channel 122 and P3 channel 123. At least one of the first detection region 1331 and the second detection region 1332 does not have a P1 channel 121. The first detection region 1331 and the second detection region 1332 respectively independently include a P2 channel 122 or a P3 channel 123, or the first detection region and the second detection region simultaneously include a P2 channel 122 and a P3 channel 123.

[0040] The method for depositing the metal top electrode 115 and the material selection for the metal top electrode 115 are both conventional choices. The metal top electrode 115 is divided by a P3 scribe line to achieve a series structure of sub-cells. In this invention, the length of the P3 scribe line is equal to the length of the TCO substrate 111.

[0041] When there is only one detection area 133, both P2 channel 122 and P3 channel 123 exist within the detection area 133. When there are two detection areas 133, one detection area 133 can contain both P2 channel 122 and P3 channel 123, while the other detection area 133 can contain only P3 channel 123. This setting ensures that both P2 channel 122 and P3 channel 123 can be detected independently, and it can also detect the situation where both P2 channel 122 and P3 channel 123 exist simultaneously, thus achieving real-time monitoring of each step.

[0042] S6. Before or after scribing P3, form a protective line at the position of the cutting line 131 that penetrates the metal top electrode 115, the functional layer and the TCO substrate 111.

[0043] Since it is necessary to isolate the detection area 133 from the effective area 132 when testing the detection area 133, a protective line is set. However, the protective line can be set before or after the P3 line is drawn. The width of the protective line is 1-5mm larger than the width of the cutting line 131 to ensure that it can completely cover the cutting line 131, avoid metal from filling the channel of the cutting line 131 and causing a short circuit, and ensure the insulation and structural integrity of the area.

[0044] The method for forming a protective line before P3 scribing includes: using a mask 134 to completely cover the area of ​​the cutting line 131, with the mask width being greater than the width of the cutting line 131; subsequently, depositing a metal top electrode 115, which covers the entire area except for the area covered by the mask 134; and then removing the mask before performing P3 scribing, with the area covered by the mask serving as the protective line. Using a mask 134 to cover the area of ​​the cutting line 131 before depositing the metal electrode prevents metal from filling the channel and causing a short circuit, ensuring regional insulation and structural integrity.

[0045] The method for forming a protective line after P3 scribing includes: after P3 scribing, laser scribing 135 pierces through all film layers at the position of cutting line 131, the width of laser scribing 135 is greater than the width of cutting line 131, and the area formed by laser scribing 135 is the protective line.

[0046] The present invention can form a protective line and completely separate the effective area 132 and the detection area 133 by using a mask template or laser scribing 135. Whether before or after scribing P3, as long as the effective area 132 and the detection area 133 P3 channel 123 can be completely separated, the specific operation method is not limited.

[0047] Since the width of the guard line is greater than the width of the cut line 131, there exists an actual effective region 1321 within the effective region 132 that is smaller than the effective region 132 (the actual effective region 1321 has a complete device structure TCO, hole transport layer 114, perovskite layer 113, electron transport layer 112, and metal top electrode 115).

[0048] S7. Measure the resistance between the left side of P2 channel 122 and the right side of P3 channel 123 in the first detection area 1331 or the second detection area 1332 containing P3 channel 123, or measure the resistance on both sides of P3 channel 123 to obtain the surface resistance of the metal electrode. Determine whether there is any metal residue in P3 channel 123 based on the value of the surface resistance of the metal electrode.

[0049] If the measured surface resistance of the metal electrode is a finite value, it indicates that there is metal electrode material remaining inside channel 123 of P3, the scribing did not completely cut off the top metal electrode, and there is a metal residue defect. If the measured surface resistance of the metal electrode exceeds the range of the detection equipment and is in an open-circuit high-resistance state, it indicates that the metal electrode in channel 123 of P3 has been completely etched away, the metal top electrode has been completely disconnected, and there is no metal residue in the channel.

[0050] First, the resistance of channel 123 in P3 is tested to determine if there is any metal residue. If metal residue is present, it indicates a short circuit risk, and the laser process should be adjusted promptly. If the surface resistance of the non-metal electrode exceeds the range of the testing equipment and is in an open-circuit high-resistance state, that is, the resistance of channel 123 in P3 tends to infinity, it indicates that P3 has successfully severed the metal top electrode, and the TCO film state needs to be further verified.

[0051] S8. After removing the functional layer of the first detection area 1331 or the second detection area 1332, measure the resistance between the left side of the P2 channel 122 and the right side of the P3 channel 123, or measure the resistance on both sides of the P3 channel 123 to obtain the TCO surface resistance; compare the TCO surface resistance with the initial TCO resistance value to determine whether the P3 scribing has damaged the TCO substrate 111. If the difference between the surface resistance of the TCO and the initial resistance of the TCO is 0-1Ω, then the test is qualified. The smaller the difference between the surface resistance of the TCO and the initial resistance of the TCO, the better the product. Specifically, when the difference between the surface resistance of the TCO and the initial resistance of the TCO is between 0 and 0.3 Ω, the product is considered excellent. When the difference between the channel resistance and the initial resistance of the TCO is between 0.3 and 1.0 Ω, it is also considered a qualified product, but there is slight burning / interface oxidation on the TCO surface, which slightly increases the contact resistance.

[0052] If the difference between the surface resistance of the TCO and the initial resistance of the TCO is greater than 1Ω or less than 0Ω, the test is unqualified and the P3 scribing parameters need to be readjusted.

[0053] When the difference between the surface resistance of TCO and the initial resistance of TCO is greater than 1Ω, it indicates that the laser over-etching has damaged the conductive layer of TCO, the local TCO has become thinner or micro-fractured, the interconnect series resistance has soared, the fill factor has deteriorated significantly, and it is directly rejected.

[0054] When the difference between the surface resistance of TCO and the initial resistance of TCO is less than 0Ω, it indicates that there is residual metal in P3 and a short circuit in the functional layer, which is also a defect.

[0055] S9. After passing the inspection, clean the edges around the effective area 132, and then encapsulate to complete the preparation of the perovskite module 100.

[0056] The area around the effective area 132 refers to cleaning the edges of the cutting lines 131 on both sides of the effective area 132, and the coating on the other two sides also needs to be cleaned to a certain extent. After cleaning, the glass substrate is retained.

[0057] The laser scribing method for perovskite modules provided by this invention shortens the P1 scribing line and, in conjunction with the scribing lines P2 and P3 and the vertical cutting line 131, partitions the TCO (Total Coefficient of Oxide) into a detection area 133 and an effective area 132, ensuring that the detection and power generation effective area 132 are independent and do not interfere with each other. The detection area 133 can be inspected in real time after the P2 and P3 scribing lines are drawn. Specifically, in the detection area 133 without P1, the channel resistance of P2 is measured to determine the conduction state of P2 and whether the TCO has been over-etched and damaged. In the detection area 133 without P1 or without P1 and P2, the metal resistance from the left side of P2 to the right side of P3 and the TCO resistance are measured to determine whether there is metal residue in P3 and whether the underlying TCO layer has been over-etched and damaged. This invention can achieve real-time, non-destructive, and quantitative detection of the scribing quality of P2 and P3 without affecting the power generation structure and performance of the effective area 132, quickly adjust laser parameters, form a closed-loop mass production process, and improve the module yield, efficiency, and reliability. It effectively solves the problems of P2 not being able to be detected online, P3 over-cutting damage TCO being difficult to verify, detection lag, and low batch yield in the process.

[0058] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0059] Example 1 This embodiment provides a real-time detectable laser scribing method for perovskite modules, which includes the following steps: S1. A P1 groove 121 is formed by scribing a P1 line on the TCO substrate 111, and the length of the P1 scribing line is simultaneously shortened by 10% on both sides (e.g., ...). Figure 3As shown in the figure, that is, the length of the P1 scribing line is 90% of the length of the TCO substrate 111), space is reserved for the cutting line 131, and the shortened P1 can still ensure the bottom electrode isolation function of the effective area 132 without affecting the series structure of the module.

[0060] S2, depositing functional layers such as a hole transport layer 114, a perovskite light-absorbing layer, and an electron transport layer 112 sequentially on the TCO substrate 111 after P1 scribing, then performing P2 scribing to form a P2 channel 122 to etch through the functional layers without damaging the TCO substrate 111, wherein the length of the P2 scribing line is greater than or equal to the length of the TCO substrate 111 (as shown in Figure 4 the figure). It covers the conduction area and lays a foundation for the effective conduction between the subsequent top electrode and the bottom electrode.

[0061] S3, preparing cutting lines 131 perpendicular to the P1 channel 121 respectively at the ends of the shortened side of the P1 scribing (as shown in Figure 5 the figure, with a width of 100 μm), the cutting lines 131 etch through the functional layers and the TCO substrate 111, and the cutting lines 131 divide the module into one effective area 132 ( Figure 6 ) and two detection areas 133 ( Figure 7 ), wherein the effective area 132 retains the complete P1 channel 121 and P2 channel 122, serving as a normal power generation area of the module, and the detection area 133 has no P1 channel 121 and only includes the P2 channel 122.

[0062] S4, measuring the channel resistance on both sides of the P2 channel 122 in the detection area 133, please refer to Figure 8 , specifically measuring at point 1 and point 2, point 2 and point 3, point 3 and point 4, point 4 and point 5 to obtain R P2 -1, R P2 -2, R P2 -3, R P2 -4 resistance values, which correspond to the resistance conditions of the 1st to 4th P2 lines. The channel resistance is compared with the initial resistance of TCO to judge the P2 etching quality; a milliohm meter is used to measure the channel resistance on both sides of the P2 channel 122. If the difference between the channel resistance and the initial resistance of TCO is 0-1Ω, the detection is qualified, indicating that the depth of P2 scribing is moderate, the underlying TCO layer is not damaged, and effective conduction can be achieved; if the difference between the channel resistance and the initial resistance of TCO is >1Ω or <0Ω, the detection is unqualified, and the P2 scribing parameters need to be readjusted. A difference greater than 1Ω indicates that the P2 scribing power is too high and the underlying TCO layer is damaged; if the resistance tends to be infinite, P2 completely etches through the underlying TCO, resulting in open circuit failure of the channel. At this time, the parameters of laser scribing 135 (such as laser power and scribing speed) need to be adjusted in time to avoid batch damage.

[0063] S5, please refer to Figure 9The area of ​​the cutting line 131 is completely covered by a mask 134, and the width of the mask is 2mm greater than the width of the cutting line 131.

[0064] S6. Subsequently, the metal top electrode 115 is deposited by vapor deposition, covering the entire area except for the area shielded by the mask 134 (see [link]). Figure 10 After removing the mask, a P3 scribe line is formed on the metal top electrode 115 to create a P3 channel 123, thus dividing the metal top electrode 115. The length of the P3 scribe line is equal to the length of the TCO substrate 111. The actual effective region 132 in the effective region 132 retains complete P1 channels 121, P2 channels 122, and P3 channels 123. The detection region 133 does not have a P1 channel 121 and only includes P2 channels 122 and P3 channels 123 (e.g., Figure 11 and Figure 12 (As shown).

[0065] S7. Measure the resistance between the left side of P2 channel 122 and the right side of P3 channel 123 in detection area 133 to obtain the surface resistance of the metal electrode. Please refer to [link / reference]. Figure 13 Measure R respectively P3 -1、R P3 -2, R P3 -3、R P3 -4 represents the surface resistance of the metal electrodes from the left side of line P2 to the right side of line P3 in lines 1-4. The value of the surface resistance of the metal electrodes is used to determine whether there is any metal residue in channel 123 of P3. If the measured surface resistance of the metal electrodes is finite, it indicates that metal electrode material remains inside channel 123 of P3, the scribe line did not completely cut off the top metal electrode, and there is a metal residue defect. If the measured surface resistance of the metal electrodes exceeds the range of the testing equipment and is in an open-circuit high-resistance state, it indicates that the metal electrode inside channel 123 of P3 has been completely etched away, the top metal electrode is completely disconnected, and there is no metal residue in the channel.

[0066] S8. After removing the functional layer of the detection area 133, the resistance between the left side of the P2 channel 122 and the right side of the P3 channel 123 is measured to obtain the TCO surface resistance. Please refer to [link / reference]. Figure 14 Detect R respectively TCO -1、R TCO -2, R TCO -3、R TCO -4 resistance value corresponds to the TCO surface resistance from the left side of P2 to the right side of P3 in lines 1-4; compare the TCO surface resistance with the initial TCO resistance value to determine whether the P3 scribing has damaged the TCO substrate 111; if the difference between the TCO surface resistance and the initial TCO resistance value is 0-1Ω, the test is qualified; if the difference between the TCO surface resistance and the initial TCO resistance value is >1Ω or <0Ω, the test is unqualified and the P3 scribing parameters need to be readjusted.

[0067] S9. After passing the inspection, clean the edges around the effective area 132, and then encapsulate to complete the preparation of the perovskite module 100.

[0068] Example 2 This embodiment is basically the same as Embodiment 1, the main difference being that in this embodiment, the line P1 is drawn by shortening one side. All other parts not mentioned are consistent with Embodiment 1. Specifically, it includes the following steps: S1. Scribing line P1 on TCO substrate 111, shortening the length of line P1 by 10% on only one side (e.g., Figure 15 (As shown).

[0069] S2, Same as in Example 1.

[0070] S3. Prepare a cutting line 131 perpendicular to the scribed line P1 at one end of the shortened side of the scribed line P1. The cutting line 131 divides the module into an effective area 132 and a detection area 133 (e.g., ...). Figure 16 (As shown).

[0071] S4-S9, Same as in Example 1, the final product is as follows: Figure 17 As shown.

[0072] Example 3 This embodiment is basically the same as embodiment 1, the main difference being that in this embodiment, the line P2 is drawn by shortening one side. All other parts not mentioned are consistent with embodiment 1. Specifically, it includes the following steps: S1 is the same as in Example 1.

[0073] S2. After depositing the functional layer, perform P2 scribing, shortening the length of one side of the P2 scribing to be flush with the P1 scribing, and extending the other end to the edge of the TCO substrate 111 (e.g., Figure 18 (As shown).

[0074] S3, please refer to Figure 19 A cutting line 131 is prepared to form an effective area 132 and two detection areas 133 (first detection area 1331 and second detection area 1332). The effective area 132 retains the complete P1 channel 121 and P2 channel 122 structure and serves as the normal power generation area of ​​the module. The first detection area 1331 has no P1 channel 121 but has a P2 channel 122 and is used for P2 channel 122 conduction detection. The second detection area 1332 has no P1 channel 121 and P2 channel 122 and is used for P3 etching damage detection (in step S3, the second detection area 1332 also has no P3 channel 123 and is a blank area).

[0075] S4. Measure the resistance on both sides of channel 122 of P2 in the first detection area 1331. The measurement method is the same as in Example 1.

[0076] S5, Same as in Example 1.

[0077] S6, please refer to Figure 20 Similar to Example 1, but in this example, the effective area 132 retains complete P1 channel 121, P2 channel 122 and P3 channel 123, the first detection area 1331 has no P1 channel 121, but has P2 channel 122 and P3 channel 123, and the second detection area 1332 has no P1 channel 121 and P2 channel 122, but has P3 channel 123.

[0078] S7, please refer to Figure 21 and Figure 22 To verify P3 etching damage, the resistance on both sides of channel 123 was measured. Utilizing the structural characteristic of the second detection area 1332 lacking P1 and P2, the resistance on both sides of channel 123 was used to determine if P3 was damaged. TCO: First, the surface resistance R of the metal electrode was measured. P3 If the resistance is low, it indicates that there is metal residue in channel 123 of P3, posing a risk of short circuit in the sub-cell, and the laser process should be adjusted promptly. If the resistance approaches infinity, it indicates that P3 has successfully severed the metal top electrode, and the TCO state needs further verification.

[0079] S8-S9 are the same as in Example 1.

[0080] Compared to Example 1, Example 3 shortens one side of P2 and incorporates a partition design to form an independent first detection area 1331 and a pure second detection area 1332 without P1 and P2. This completely eliminates the interference of the P2 channel 122 resistance on the P3 detection results, enabling independent and accurate determination of P2 scribing quality and P3 etching damage. This effectively improves detection accuracy and reliability. At the same time, the partition structure is clearer, the test points are easier to locate, and it is more suitable for mass production automated testing and full-process quality control.

[0081] Example 4 This embodiment is basically the same as embodiment 1, the main difference being that in embodiment 1, a protective line is formed using a mask 134 before P3 scribing, while in this embodiment, a secondary laser scribing 135 replaces the mask 134 to form a protective line after P3 scribing, specifically including the following steps: S1-S4 are the same as in Example 1.

[0082] S5, please refer to Figure 23 The metal top electrode 115 is deposited directly without the need for a mask 134, and the metal top electrode 115 covers the entire area. P3 lines are then drawn on the metal top electrode 115.

[0083] S6, please refer to Figure 24A protective line is prepared using a secondary laser scribing technique 135. The protective line is positioned at the same level as the cutting line 131, but its width is slightly wider than that of the cutting line 131. The protective line pierces through all film layers, completely separating the effective area 132 from the detection area 133.

[0084] S7-S9 are the same as in Example 1.

[0085] In this embodiment, laser secondary scribing replaces the mask 134 process, eliminating the need for mask alignment and occlusion allowances. This allows for precise control of the trench line width, avoids redundant invalid areas caused by mask offset, significantly reduces the series dead zone area, and effectively reduces the loss of effective power generation area of ​​the perovskite module. At the same time, laser secondary scribing is compatible with all the above embodiments.

[0086] In summary, the real-time detection method for laser scribing of perovskite modules provided by this invention shortens the P1 scribing line and, in conjunction with the scribing lines P2 and P3 and the vertical cutting line 131, partitions the TCO into a detection area 133 and an effective area 132, ensuring that the detection and power generation effective area 132 are independent and do not interfere with each other. The detection area 133 can be inspected in real time after the P2 and P3 scribing lines are drawn. Specifically, in the detection area 133 without P1, the channel resistance of P2 is measured to determine the conduction state of P2 and whether the TCO has been over-etched and damaged. In the detection area 133 without P1 or without P1 and P2, the metal resistance from the left side of P2 to the right side of P3 and the TCO resistance are measured to determine whether there is metal residue in P3 and whether the underlying TCO layer has been over-etched and damaged. This invention can achieve real-time, non-destructive, and quantitative detection of the scribing quality of P2 and P3 without affecting the power generation structure and performance of the effective area 132, quickly adjust laser parameters, form a closed-loop mass production process, and improve module yield, efficiency, and reliability. It effectively solves the problems of P2 not being able to be detected online, P3 over-cutting damage TCO being difficult to verify, detection lag, and low batch yield in the process.

[0087] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A real-time detectable laser scribing method for perovskite modules, characterized in that, It includes: P1 channels are formed by scribing P1 lines on a TCO substrate, wherein the length of the P1 scribing lines is less than the length of the TCO substrate. A functional layer is deposited on the TCO substrate after the P1 scribing, and then a P2 scribing is performed to form a P2 channel. The P2 channel scribes through the functional layer without damaging the TCO substrate. The length of the P2 scribing is greater than the length of the P1 scribing and less than or equal to the length of the TCO substrate. A cutting line perpendicular to the P1 channel is prepared at the shortened end of the P1 scribe line. The cutting line pierces through the functional layer and the TCO substrate. The cutting line divides the module into an effective area, a first detection area, and a second detection area. The lengths of the first detection area and the second detection area are not both 0. The effective area retains complete P1 and P2 channels. At least one of the first and second detection areas does not have a P1 channel and only includes a P2 channel. The channel resistance on both sides of the P2 channel is measured in the first detection area or the second detection area containing the P2 channel, and the channel resistance is compared with the initial resistance value of TCO to determine the etching quality of the P2 scribing. Subsequently, a metal top electrode is deposited by vapor deposition. A P3 channel is formed on the metal top electrode by scribe lines to divide the metal top electrode. The length of the P3 scribe line is greater than the length of the P1 scribe line and less than or equal to the length of the TCO substrate. The effective area retains complete P1, P2, and P3 channels. At least one of the first detection area and the second detection area does not have a P1 channel. The first detection area and the second detection area each independently include a P2 channel or a P3 channel, or the first detection area and the second detection area simultaneously include both P2 and P3 channels. Before or after the P3 scribing, a protective line is formed at the location of the scribe line, penetrating the metal top electrode, the functional layer, and the TCO substrate; The resistance between the left side of the P2 channel and the right side of the P3 channel is measured in the first detection area or the second detection area containing the P3 channel, or the resistance on both sides of the P3 channel is measured to obtain the surface resistance of the metal electrode. The presence or absence of metal residue in the P3 channel is determined based on the value of the surface resistance of the metal electrode. After removing the functional layer of the first or second detection area, the resistance between the left side of the P2 channel and the right side of the P3 channel is measured, or the resistance on both sides of the P3 channel is measured to obtain the TCO surface resistance; the TCO surface resistance is compared with the initial resistance value of the TCO to determine whether the P3 channel has damaged the TCO substrate. After passing the inspection, the edges of the effective area are cleaned, and then the perovskite module is packaged to complete the preparation.

2. The real-time detectable laser scribing method for perovskite modules according to claim 1, characterized in that, The length of the P1 scribe line is 70%-95% of the length of the TCO substrate.

3. The real-time detectable laser scribing method for perovskite modules according to claim 1, characterized in that, The length of the P1 line can be adjusted by shortening it on one side or by shortening it simultaneously on both sides.

4. The real-time detectable laser scribing method for perovskite modules according to claim 1, characterized in that, The width of the cutting line is 5-200μm.

5. The real-time detectable laser scribing method for perovskite modules according to claim 1, characterized in that, The width of the protective line is 1-5 mm larger than the width of the cutting line.

6. The real-time detectable laser scribing method for perovskite modules according to claim 5, characterized in that, The method for forming the protective line before the P3 scribing includes: using a mask to completely cover the area of ​​the cutting line, the width of the mask being greater than the width of the cutting line; subsequently depositing the metal top electrode, the metal top electrode covering the entire area except for the area covered by the mask; removing the mask and then performing the P3 scribing, the area covered by the mask being the protective line.

7. The real-time detectable laser scribing method for perovskite modules according to claim 5, characterized in that, The method for forming the protective line after the P3 scribing includes: after the P3 scribing, scribing through all film layers at the position of the cutting line with a laser, wherein the width of the laser scribing is greater than the width of the cutting line, and the area formed by the laser scribing is the protective line.

8. The real-time detectable laser scribing method for perovskite modules according to claim 1, characterized in that, The step of comparing the channel resistance with the initial resistance value of TCO to determine the P2 etching quality includes: If the difference between the channel resistance and the initial resistance of the TCO is 0-1Ω, then the test is qualified; If the difference between the channel resistance and the initial resistance of the TCO is greater than 1Ω or less than 0Ω, the test is unqualified and the P2 scribing parameters need to be readjusted.

9. The real-time detectable laser scribing method for perovskite modules according to claim 1, characterized in that, The steps for determining whether there is metal residue in the P3 channel based on the surface resistance value of the metal electrode include: If the surface resistance of the metal electrode is measured to be a finite value, it indicates that metal electrode material remains inside the P3 channel, the scribing did not completely cut off the metal top electrode, and there is a metal residue defect. If the measured surface resistance of the metal electrode exceeds the range of the detection equipment and is in an open-circuit high-resistance state, it indicates that the metal electrode in the P3 channel has been completely etched away, the metal top electrode is completely disconnected, and there is no metal residue in the channel.

10. The real-time detectable laser scribing method for perovskite modules according to claim 1, characterized in that, The step of comparing the surface resistance of the TCO with the initial resistance value of the TCO to determine whether the P3 scribing has damaged the TCO substrate includes: If the difference between the surface resistance of the TCO and the initial resistance of the TCO is 0-1Ω, then the test is qualified. If the difference between the surface resistance of the TCO and the initial resistance of the TCO is greater than 1Ω or less than 0Ω, the test is unqualified and the P3 scribing parameters need to be readjusted.

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